Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Nanoengineered aqueous-hydrotrope hybrid liquid electrolyte solutions for efficient zinc batteries across a wide temperature range

Nature Nanotechnology volume 21, pages 95–105 (2026)Cite this article

Subjects

Abstract

Aqueous zinc metal batteries are ideal candidates for grid storage applications. However, their practical application is hindered by a narrow operating temperature range and a limited electrolyte electrochemical stability window, both of which can be attributed to the water activity. Here, to minimize water activity in the electrolyte solution, we introduce a nanoengineered approach in which the water molecules are confined within a hydrophilic–hydrophobic water solvation sheath. The hydrogen-bond interaction with the hydrophilic groups in the inner solvation layer effectively suppresses water decomposition, and the hydrophobic solvents in the outer solvation layer establish a repulsive effect against water molecules. As a proof of concept, a hydrophobic and non-polar hydrofluoroether cosolvent is introduced into a Zn-ion aqueous electrolyte solution and tested together with various fluorinated hydrotrope molecules to favour the compatibility of the cosolvent with water. By such a water confinement strategy, an average Zn plating/stripping reversibility of 99.92% is achieved for over 4,000 cycles at 2.0 mA cm−2 and 2.0 mAh cm−2 in a Zn||Cu coin cell configuration. When tested in a Zn||VOPO4·2H2O lab-scale cell configuration, the selected aqueous-hydrotrope hybrid electrolyte solution enables long-lasting and highly reversible battery performance across temperatures from −80 °C to +60 °C.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Nanoengineered design of the gradient water solvation strategy.
Fig. 2: Phase diagram and structural investigations of the aqueous-hydrotrope hybrid electrolyte solutions.
Fig. 3: Fundamental investigation on the evolution of water solvation in various hybrid electrolyte solutions.
Fig. 4: Basic electrochemical characterizations of the various electrolyte formulations.
Fig. 5: Physicochemical investigations on the Zn-ion desolvation and Zn|electrolyte interfacial processes.
Fig. 6: Zn||VOPO4·2H2O coin and pouch cell testing at various temperatures.

Similar content being viewed by others

Data availability

All data supporting the findings of this study are available in the article and its Supplementary Information. Source data are provided with this paper.

References

  1. Mathlouthi, M. Water content, water activity, water structure and the stability of foodstuffs. Food Control 12, 409–417 (2001).

    Article  Google Scholar 

  2. Sheng, D. et al. Hydrogen bond network regulation in electrolyte structure for Zn-based aqueous batteries. Adv. Funct. Mater. 34, 2402014 (2024).

    Article  CAS  Google Scholar 

  3. Wang, Y. et al. Enabling high-energy-density aqueous batteries with hydrogen bond-anchored electrolytes. Matter 5, 162–179 (2022).

    Article  CAS  Google Scholar 

  4. Roy, K., Rana, A., Heil, J. N., Tackett, B. M. & Dick, J. E. For zinc metal batteries, how many electrons go to hydrogen evolution? An electrochemical mass spectrometry study. Angew. Chem. Int. Ed. 63, e202319010 (2024).

    Article  CAS  Google Scholar 

  5. Emamian, S., Lu, T., Kruse, H. & Emamian, H. Exploring nature and predicting strength of hydrogen bonds: a correlation analysis between atoms-in-molecules descriptors, binding energies, and energy components of symmetry-adapted perturbation theory. J. Comput. Chem. 40, 2868–2881 (2019).

    Article  CAS  PubMed  Google Scholar 

  6. Li, M. et al. Comprehensive understandings of hydrogen bond chemistry in aqueous batteries. Adv. Mater. 36, 2308628 (2024).

    Article  CAS  Google Scholar 

  7. Wang, F. et al. Highly reversible zinc metal anode for aqueous batteries. Nat. Mater. 17, 543–549 (2018).

    Article  CAS  PubMed  Google Scholar 

  8. Lim, J. et al. Nanometric water channels in water-in-salt lithium ion battery electrolyte. J. Am. Chem. Soc. 140, 15661–15667 (2018).

    Article  CAS  PubMed  Google Scholar 

  9. Zhang, M. et al. Understanding the microscopic structure of a “water-in-salt” lithium ion battery electrolyte probed with ultrafast IR spectroscopy. J. Phys. Chem. C 124, 8594–8604 (2020).

    Article  CAS  Google Scholar 

  10. Hao, J. et al. Boosting zinc electrode reversibility in aqueous electrolytes by using low-cost antisolvents. Angew. Chem. Int. Ed. 60, 7366–7375 (2021).

    Article  CAS  Google Scholar 

  11. Wang, W. et al. Regulating interfacial reaction through electrolyte chemistry enables gradient interphase for low-temperature zinc metal batteries. Nat. Commun. 14, 5443 (2023).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. Ming, F. et al. Co-solvent electrolyte engineering for stable anode-free zinc metal batteries. J. Am. Chem. Soc. 144, 7160–7170 (2022).

    Article  CAS  PubMed  Google Scholar 

  13. Robertson, A. E. et al. Mesoscale solubilization and critical phenomena in binary and quasi-binary solutions of hydrotropes. Fluid Phase Equilib. 407, 243–254 (2016).

    Article  CAS  Google Scholar 

  14. Kunz, W., Holmberg, K. & Zemb, T. Hydrotropes. Curr. Opin. Colloid Interface Sci. 22, 99–107 (2016).

    Article  CAS  Google Scholar 

  15. Dukhin, A. & Pavlenishvilli, D. “Water-in-salt” super concentrated electrolyte clusters are “micelles”. Colloids Surf. A 678, 132466 (2023).

    Article  CAS  Google Scholar 

  16. Miao, L. et al. Aqueous electrolytes with hydrophobic organic cosolvents for stabilizing zinc metal anodes. ACS Nano 16, 9667–9678 (2022).

    Article  CAS  PubMed  Google Scholar 

  17. Dong, Y. et al. Non-concentrated aqueous electrolytes with organic solvent additives for stable zinc batteries. Chem. Sci. 12, 5843–5852 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  18. Bauduin, P., Renoncourt, A., Kopf, A., Touraud, D. & Kunz, W. Unified concept of solubilization in water by hydrotropes and cosolvents. Langmuir 21, 6769–6775 (2005).

    Article  CAS  PubMed  Google Scholar 

  19. Dong, D., Wang, T., Sun, Y., Fan, J. & Lu, Y.-C. Hydrotropic solubilization of zinc acetates for sustainable aqueous battery electrolytes. Nat. Sustain. 6, 1474–1484 (2023).

    Article  Google Scholar 

  20. Zhao, Z. et al. A novel “water-in-ionic liquid” electrolyte for Zn metal batteries. ACS Energy Lett. 8, 608–618 (2023).

    Article  CAS  Google Scholar 

  21. Amann-Winkel, K. et al. X-ray and neutron scattering of water. Chem. Rev. 116, 7570–7589 (2016).

    Article  CAS  PubMed  Google Scholar 

  22. Zheng, J. et al. Understanding thermodynamic and kinetic contributions in expanding the stability window of aqueous electrolytes. Chem 4, 2872–2882 (2018).

    Article  CAS  Google Scholar 

  23. Zhang, C. et al. The electrolyte comprising more robust water and superhalides transforms Zn-metal anode reversibly and dendrite-free. Carbon Energy 3, 339–348 (2021).

    Article  Google Scholar 

  24. Yang, W., Yang, Y., Yang, H. & Zhou, H. Regulating water activity for rechargeable zinc-ion batteries: progress and perspective. ACS Energy Lett. 7, 2515–2530 (2022).

    Article  CAS  Google Scholar 

  25. Miyazaki, K. et al. First-principles study on the peculiar water environment in a hydrate-melt electrolyte. J. Phys. Chem. Lett. 10, 6301–6305 (2019).

    Article  CAS  PubMed  Google Scholar 

  26. Subramanian, D., Boughter, C. T., Klauda, J. B., Hammouda, B. & Anisimov, M. A. Mesoscale inhomogeneities in aqueous solutions of small amphiphilic molecules. Faraday Discuss. 167, 217–238 (2013).

    Article  PubMed  Google Scholar 

  27. Huang, Z. et al. Anion chemistry in energy storage devices. Nat. Rev. Chem. 7, 616–631 (2023).

    Article  PubMed  Google Scholar 

  28. Zhang, Y. et al. Suppressed dissolution of fluorine-rich SEI enables highly reversible zinc metal anodes for stable aqueous zinc-ion batteries. Angew. Chem. Int. Ed. 136, e202407067 (2024).

    Article  Google Scholar 

  29. Shi, H.-Y. et al. Inhibiting VOPO4⋅xH2O decomposition and dissolution in rechargeable aqueous zinc batteries to promote voltage and capacity stabilities. Angew. Chem. Int. Ed. 58, 16057–16061 (2019).

    Article  CAS  Google Scholar 

  30. Liu, S. et al. From room temperature to harsh temperature applications: fundamentals and perspectives on electrolytes in zinc metal batteries. Sci. Adv. 8, eabn5097 (2022).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  31. Borodin, O. et al. Liquid structure with nano-heterogeneity promotes cationic transport in concentrated electrolytes. ACS Nano 11, 10462–10471 (2017).

    Article  CAS  PubMed  Google Scholar 

  32. Cao, L. et al. Fluorinated interphase enables reversible aqueous zinc battery chemistries. Nat. Nanotechnol. 16, 902–910 (2021).

    Article  CAS  PubMed  Google Scholar 

  33. Yang, C. et al. All-temperature zinc batteries with high-entropy aqueous electrolyte. Nat. Sustain. 6, 325–335 (2023).

    Article  Google Scholar 

  34. Cong, J. et al. Kinetics compensation mechanism in cosolvent electrolyte strategy for aqueous zinc batteries. J. Am. Chem. Soc. https://doi.org/10.1021/jacs.4c16880 (2025).

    Article  PubMed  PubMed Central  Google Scholar 

  35. Wang, Y. et al. Sulfolane-containing aqueous electrolyte solutions for producing efficient ampere-hour-level zinc metal battery pouch cells. Nat. Commun. 14, 1828 (2023).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  36. Liang, G. et al. Regulating inorganic and organic components to build amorphous-ZnFx enriched solid–electrolyte interphase for highly reversible Zn metal chemistry. Adv. Mater. 35, 2210051 (2023).

    Article  CAS  Google Scholar 

  37. Chang, N. et al. An aqueous hybrid electrolyte for low-temperature zinc-based energy storage devices. Energy Environ. Sci. 13, 3527–3535 (2020).

    Article  CAS  Google Scholar 

  38. Wang, S. et al. Fast reaction kinetics and commendable low-temperature adaptability of zinc batteries enabled by aprotic water–acetamide symbiotic solvation sheath. Angew. Chem. Int. Ed. 63, e202316841 (2024).

    Article  CAS  Google Scholar 

  39. Qiu, Y. et al. Möbius solvation structure for zinc-ion batteries. Adv. Mater. 37, e2415373 (2025).

    Article  PubMed  Google Scholar 

  40. Cao, X. et al. Weak solvation effect induced optimal interfacial chemistry enables highly durable Zn anodes for aqueous Zn-ion batteries. Angew. Chem. Int. Ed. 63, e202317302 (2024).

    Article  CAS  Google Scholar 

  41. Shi, J. et al. “Water-in-deep eutectic solvent” electrolytes for high-performance aqueous Zn-ion batteries. Adv. Funct. Mater. 31, 2102035 (2021).

    Article  CAS  Google Scholar 

  42. Xie, D. et al. ZnF2-riched inorganic/organic hybrid SEI: in situ-chemical construction and performance-improving mechanism for aqueous zinc-ion batteries. Angew. Chem. Int. Ed. 62, e202216934 (2023).

    Article  CAS  Google Scholar 

  43. Sun, P. et al. Simultaneous regulation on solvation shell and electrode interface for dendrite-free Zn ion batteries achieved by a low-cost glucose additive. Angew. Chem. Int. Ed. 133, 18395–18403 (2021).

    Article  Google Scholar 

  44. Jin, Y. et al. Stabilizing zinc anode reactions by polyethylene oxide polymer in mild aqueous electrolytes. Adv. Funct. Mater. 30, 2003932 (2020).

    Article  CAS  Google Scholar 

  45. Chen, Y. et al. Low current-density stable zinc-metal batteries via aqueous/organic hybrid electrolyte. Batter. Supercaps 5, e202200001 (2022).

    Article  CAS  Google Scholar 

  46. Wang, D. et al. Solvation modulation enhances anion-derived solid electrolyte interphase for deep cycling of aqueous zinc metal batteries. Angew. Chem. Int. Ed. 62, e202310290 (2023).

    Article  CAS  Google Scholar 

  47. Zhou, A. et al. Molecular recognition effect enabled by novel crown ether as macrocyclic host towards highly reversible Zn anode. Sci. Bull. 68, 2170–2179 (2023).

    Article  CAS  Google Scholar 

  48. Wan, F. et al. Reversible oxygen redox chemistry in aqueous zinc-ion batteries. Angew. Chem. Int. Ed. 58, 7062–7067 (2019).

    Article  CAS  Google Scholar 

  49. Terban, M. W. & Billinge, S. J. Structural analysis of molecular materials using the pair distribution function. Chem. Rev. 122, 1208–1272 (2021).

    Article  PubMed  PubMed Central  Google Scholar 

  50. Egami, T. & Billinge, S. J. Underneath the Bragg Peaks: Structural Analysis of Complex Materials 16 (Elsevier, 2003).

  51. Gaussian 16 Rev. B.01 (Gaussian, 2016).

  52. Lu, T. & Chen, F. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580–592 (2012).

    Article  PubMed  Google Scholar 

  53. Boys, S. F. & Bernardi, F. The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Mol. Phys. 19, 553–566 (1970).

    Article  CAS  Google Scholar 

  54. Pan, J., Zhang, Q., Xiao, X., Cheng, Y.-T. & Qi, Y. Design of nanostructured heterogeneous solid ionic coatings through a multiscale defect model. ACS Appl. Mater. Interfaces 8, 5687–5693 (2016).

    Article  CAS  PubMed  Google Scholar 

  55. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).

    Article  CAS  Google Scholar 

  56. Martínez, L., Andrade, R., Birgin, E. G. & Martínez, J. M. PACKMOL: a package for building initial configurations for molecular dynamics simulations. J. Comput. Chem. 30, 2157–2164 (2009).

    Article  PubMed  Google Scholar 

  57. Mark, P. & Nilsson, L. Structure and dynamics of the TIP3P, SPC, and SPC/E water models at 298 K. J. Phys. Chem. A 105, 9954–9960 (2001).

    Article  CAS  Google Scholar 

  58. Zhu, X., Lopes, P. E. & MacKerell, A. D. Jr Recent developments and applications of the CHARMM force fields. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2, 167–185 (2012).

    Article  CAS  PubMed  Google Scholar 

  59. Zielkiewicz, J. Structural properties of water: comparison of the SPC, SPCE, TIP4P, and TIP5P models of water. J. Chem. Phys. 123, 104501 (2005).

    Article  PubMed  Google Scholar 

  60. Obst, S. & Bradaczek, H. Molecular dynamics simulations of zinc ions in water using CHARMM. Mol. Model. Annu. 3, 224–232 (1997).

    Article  CAS  Google Scholar 

  61. Patil, N. et al. An ultrahigh performance zinc-organic battery using poly (catechol) cathode in Zn (TFSI)2-based concentrated aqueous electrolytes. Adv. Energy Mater. 11, 2100939 (2021).

    Article  CAS  Google Scholar 

  62. Canongia Lopes, J. N. & Pádua, A. A. CL&P: a generic and systematic force field for ionic liquids modeling. Theor. Chem. Acc. 131, 1–11 (2012).

    Article  CAS  Google Scholar 

  63. Schauperl, M. et al. Non-bonded force field model with advanced restrained electrostatic potential charges (RESP2). Commun. Chem. 3, 44 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  64. Humphrey, W., Dalke, A. & Schulten, K. VMD: visual molecular dynamics. J. Mol. Graph. 14, 33–38 (1996).

    Article  CAS  PubMed  Google Scholar 

  65. Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).

    Article  CAS  Google Scholar 

  66. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).

    Article  CAS  Google Scholar 

  67. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558 (1993).

    Article  CAS  Google Scholar 

  68. Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251 (1994).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank the grant from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project Number CityU C1002-21G; C.Z.). We also acknowledge the Shanghai Synchrotron Radiation Facility (SSRF) and European Synchrotron Radiation Facility (ESRF) for the provision of synchrotron radiation facilities. We thank the Momentum Transfer team for facilitating the measurements and J. Drnec for assistance and support in using beamline ID31. The measurement set-up was developed with funding from the European Union’s Horizon 2020 Research and Innovation programme under the STREAMLINE project (grant agreement ID870313; W.H.K.). We acknowledge the support from Shanghai Pilot Program for Basic Research (W.L.), Xiaomi Young Talents Program (W.L. and X.F.), and the National Natural Science Foundation of China (W2432001; W.H.K.), (U21A2081; X.F.) and (52027816; Y.H.).

Author information

Author notes

  1. These authors contributed equally: Xueying Zheng, Haotian Zhu, Zhongqiang Wang, Hua Yang.

Authors and Affiliations

  1. Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, China

    Xueying Zheng, Huilin Cui & Chunyi Zhi

  2. State Key Laboratory of Silicon and Advanced Semiconductor Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou, China

    Haotian Zhu, Ruhong Li, Haikuo Zhang, Jinze Wang & Xiulin Fan

  3. Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai, China

    Zhongqiang Wang, Wei Luo & Yiming Dai

  4. Spallation Neutron Source Science Center, Dongguan, China

    Hua Yang & Wang Hay Kan

  5. Institute of High Energy Physics, Chinese Academy of Sciences (CAS), Beijing, China

    Hua Yang & Wang Hay Kan

  6. Centre for Energy Storage, The University of Hong Kong, Hong Kong, China

    Chunyi Zhi

  7. Department of Mechanical Engineering, The University of Hong Kong, Hong Kong, China

    Chunyi Zhi

  8. State Key Laboratory of Material Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, China

    Yunhui Huang

Authors
  1. Xueying Zheng
    View author publications

    Search author on:PubMed Google Scholar

  2. Haotian Zhu
    View author publications

    Search author on:PubMed Google Scholar

  3. Zhongqiang Wang
    View author publications

    Search author on:PubMed Google Scholar

  4. Hua Yang
    View author publications

    Search author on:PubMed Google Scholar

  5. Ruhong Li
    View author publications

    Search author on:PubMed Google Scholar

  6. Wei Luo
    View author publications

    Search author on:PubMed Google Scholar

  7. Wang Hay Kan
    View author publications

    Search author on:PubMed Google Scholar

  8. Yiming Dai
    View author publications

    Search author on:PubMed Google Scholar

  9. Haikuo Zhang
    View author publications

    Search author on:PubMed Google Scholar

  10. Jinze Wang
    View author publications

    Search author on:PubMed Google Scholar

  11. Huilin Cui
    View author publications

    Search author on:PubMed Google Scholar

  12. Xiulin Fan
    View author publications

    Search author on:PubMed Google Scholar

  13. Chunyi Zhi
    View author publications

    Search author on:PubMed Google Scholar

  14. Yunhui Huang
    View author publications

    Search author on:PubMed Google Scholar

Contributions

X.Z., W.L., X.F. and C.Z. conceived of the idea and designed the experiments. H. Zhu, R.L., H. Zhang and J.W. performed the theoretical simulations. X.Z., Z.W., Y.D. and H.C. carried out the characterizations and electrochemical measurements. H.Y. and W.H.K. performed the synchrotron-based characterizations and analysis. X.Z., H. Zhu and C.Z. drafted the paper with input from all co-authors. X.Z., H. Zhu, R.L., H. Zhang, W.L., X.F., C.Z., W.H.K. and Y.H. contributed to the scientific discussion and data interpretation. All authors have read and approved the final version of the paper.

Corresponding authors

Correspondence to Wei Luo, Wang Hay Kan, Xiulin Fan, Chunyi Zhi or Yunhui Huang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Nanotechnology thanks Kyeounghak Kim, Dipan Kundu and Nian Liu for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information (download PDF )

Supplementary Figs. 1–77, Tables 1–6, Notes 1–47 and References.

Source data

Source Data Fig. 1 (download XLSX )

Statistical source data for Fig. 1.

Source Data Fig. 2 (download XLSX )

Statistical source data for Fig. 2.

Source Data Fig. 3 (download XLSX )

Statistical source data for Fig. 3.

Source Data Fig. 4 (download XLSX )

Statistical source data for Fig. 4.

Source Data Fig. 5 (download XLSX )

Statistical source data for Fig. 5.

Source Data Fig. 6 (download XLSX )

Statistical source data for Fig. 6.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zheng, X., Zhu, H., Wang, Z. et al. Nanoengineered aqueous-hydrotrope hybrid liquid electrolyte solutions for efficient zinc batteries across a wide temperature range. Nat. Nanotechnol. 21, 95–105 (2026). https://doi.org/10.1038/s41565-025-02060-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41565-025-02060-6

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing